A three-dimensional off-lattice kinetic Monte Carlo-Molecular Dynamics (KMC-MD) simulation framework [Comp. Mat. Sci. 229, 112421 (2023)] is used to investigate the dehydrochlorination (DHC) transformation of polyvinyl chloride (PVC) in sodium hydroxide (NaOH) with atomistic resolutions at experimental timescales (103 – 106 s). Our framework enables an examination of the competing reaction pathways and molecular-scale changes influenced by various solvents (acetone, ethylene glycol, triethylene glycol, tetrahydrofuran (THF), and bio-derived solvents). The algorithm simulates bond cleavage and formation during the KMC stages, whereas the MD stage is dedicated to the relaxation and thermalization of the PVC-NaOH-solvent system. Our findings reveal that the solvent-induced precipitation of NaOH plays a dominant role in the DHC process. THF produced the highest % DHC (24%) of PVC in 1 M NaOH at 300 K, due to its rapid diffusion of NaOH molecules, initial surface area expansion, and appreciable increase in intensity of PVC-NaOH interactions over the course of the reaction. Overall, the KMC-MD framework captures important configurational details not accessible with a traditional microkinetic model and enables benchmarking at experimental timescales.